Coated article having protective coating containing silicon nitride and / or silicon oxynitride

Abstract

To reduce or avoid these defects in a coating stack.SOLUTION: A coated article includes a substrate, a functional layer over at least a portion of the substrate, and a protective coating over at least a portion of the functional layer, where an uppermost layer of the functional layer is a metal oxide layer, and where the protective coating comprises a metal nitride layer and a metal oxynitride layer that is disposed between, and in contact with at least part of, the metal nitride layer and the metal oxide layer of the functional layer.SELECTED DRAWING: None

Description

Technical Field

[0001] Cross - Reference to Related Applications This application claims the benefit of U.S. Provisional Patent Application No. 62 / 631,283, filed Feb. 15, 2018; U.S. Provisional Patent Application No. 62 / 631,588, filed Feb. 16, 2018; and U.S. Provisional Patent Application No. 62 / 734,656, filed Sep. 21, 2018, each of which is incorporated herein by reference in its entirety.

[0002] The invention according to the present disclosure generally relates to a solar control coating having a top coat including a metal nitride layer and / or a metal oxynitride disposed on a metal oxide layer.

Background Art

[0003] Coating stacks of coated articles can corrode over time. To prevent this, a protective coating can be applied to the coating stack. For example, the titanium dioxide films disclosed in U.S. Pat. No. 4,716,086 and U.S. Pat. No. 4,786,563 are protective films that provide chemical resistance to the coating. Silicon oxide disclosed in Canadian Patent No. 2,156,571, aluminum oxide and silicon nitride disclosed in U.S. Pat. No. 5,425,861, U.S. Pat. No. 5,344,718, U.S. Pat. No. 5,376,455, U.S. Pat. No. 5,584,902, U.S. Pat. No. 5,532,180 and PCT International Patent Publication No. 95 / 29883 are also protective films that provide chemical resistance to the coating. This technology may be advanced by more chemically and / or mechanically durable coatings.

[0004] Additional known problems related to coating stacks including protective coatings occur with silver-based coating stacks. In certain coated articles, the upper layer of the functional coating includes a metal oxide layer such as a zinc oxide layer and is disposed over the terminal metal-prime layer of the functional coating. This can cause corrosion or brilliance defects in the stack when exposed to a humid environment with condensed moisture for an extended period of time. Accordingly, there is a further need to reduce or avoid these defects in the coating stack. SUMMARY OF THE INVENTION

[0005] According to one aspect of the invention, a coated article is provided. The coated article includes a substrate, a first functional layer over at least a portion of the substrate, and a protective coating over at least a portion of the functional layer, wherein the topmost layer of the functional layer is a metal oxide film and the protective coating includes one or more layers of a metal nitride, a metal oxynitride, or a combination thereof.

[0006] In one aspect, the coated article includes a glass substrate, a layer of zinc stannate over at least a portion of the glass substrate, a layer of zinc oxide over at least a portion of the layer of zinc stannate, a layer of silver over at least a portion of the layer of zinc oxide, a primer layer including Ti, TiAl, and / or an oxide thereof over at least a portion of the layer of silver, a second layer of zinc stannate over at least a portion of the primer layer, a metal oxynitride layer including silicon oxynitride directly over at least a portion of the second layer of zinc stannate, a metal nitride layer including silicon directly over at least a portion of the metal oxynitride layer, and a second protective layer including Ti, TiAl, and / or an oxide of any of the foregoing over at least a portion of the metal nitride layer.

[0007] In another aspect, a coated article is provided. The coated article includes a substrate, a functional layer having a topmost layer over at least a portion of the substrate, and a protective coating over at least a portion of the functional layer, wherein the topmost layer of the functional layer is a dielectric layer having a refractive index of at least 1.5 and no greater than 2.1.

[0008] In another aspect, a coated article is provided that includes a substrate, a functional layer on at least a portion of the substrate, and a protective coating on at least a portion of the functional layer, the functional layer including at least one metal layer and a primer layer disposed at least partially in contact on at least a portion of the at least one metal layer, an uppermost layer of the functional layer being disposed in contact on at least a portion of the primer layer, and the uppermost layer of the functional layer not including zinc oxide.

[0009] The present invention is described with reference to the following drawings, with like reference numerals identifying like parts throughout. BRIEF DESCRIPTION OF THE DRAWINGS

[0010]

Figure 1A

[0011]

Figure 1B

[0012]

Figure 2A

Figure 2B

[0013]

Figure 3

[0014]

Figure 4A

Figure 4B

[0015]

Figure 5

[0016]

Figure 6

DETAILED DESCRIPTION OF THE INVENTION

[0017] As used herein, spatial or directional terms such as "left", "right", "inner", "outer", "upper", "lower", etc. are related to the present invention as shown in the drawings. However, it should be understood that the present invention can assume various alternative orientations, and thus such terms should not be considered limiting. Further, as used herein, all numbers representing dimensions, physical properties, processing parameters, amounts of components, reaction conditions, etc. used in the specification and claims are to be understood as being modified in all cases by the term "about". Accordingly, unless indicated to the contrary, the numerical values set forth in the following specification and claims can vary depending on the desired properties to be obtained by the present invention. At a minimum, and not as an attempt to limit the application of the doctrine of equivalents to the claims, each numerical value should be construed at least in light of the number of reported significant digits and by applying ordinary rounding technique. Further, all ranges disclosed herein are to be understood to include the starting and ending range values, as well as every sub-range subsumed therein. For example, a specified range of "1 to 10" includes every sub-range between and including the minimum value 1 and the maximum value 10, i.e., every sub-range that begins with a minimum value of 1 or more and ends with a maximum value of 10 or less, such as 1 to 3.3, 4.7 to 7.5, 5.5 to 10, etc. "A" or "an" refers to one or more.

[0018] Furthermore, as used herein, the terms "formed over", "deposited over", or "provided over" mean formed, deposited, or provided but not necessarily in contact with the surface. For example, a coating layer "formed over" a substrate does not exclude the presence of one or more other coating layers or films of the same or different composition located between the formed coating layer and the substrate. Further, all documents referred to herein, such as but not limited to issued patents and patent applications, should be considered to be "incorporated by reference" in their entirety. As used herein, the term "film" refers to a coated area of a desired or selected coating composition. A "layer" can include one or more "films", and a "coating" or "coating stack" can include one or more "layers". The term "asymmetrical reflectivity" means that the visible light reflectivity of a coating from one side is different from the visible light reflectivity of the coating from the opposite side. The term "critical thickness" means the thickness at which, when exceeded, the coating material forms a continuous, unbroken layer, and below which the coating material forms discontinuous regions or islands of coating material rather than a continuous layer. The term "subcritical thickness" means a thickness below the critical thickness such that the coating material forms separated, non-connected regions of coating material. The term "islanded" means that the coating material does not form a continuous layer, but rather the material is deposited to form isolated regions or islands.

[0019] For the purposes of the following discussion, the coated articles described herein can be discussed with respect to use with architectural transparencies such as, but not limited to, insulated glass units (IGUs). As used herein, the term "architectural transparency" refers to any transparency disposed in a building such as, but not limited to, windows and skylights. However, the coated articles described herein are not limited to use with such architectural transparencies and can be implemented with transparencies in any desired field, such as, but not limited to, laminated or non-laminated residential and / or commercial windows, insulated glass units, and / or transparencies for land, air, space, water, and underwater vehicles. In one aspect or embodiment, the coated articles described herein are transparencies for use in vehicles such as windows or sunroofs. Accordingly, it should be understood that the specifically disclosed exemplary aspects or embodiments are presented merely to illustrate the general concepts of the invention and that the invention is not limited to these particular exemplary embodiments. Further, a typical "transparency" can have a sufficient visible light transmittance such that materials can be seen through the transparency, but a "transparency" need not be transparent to visible light and can be translucent or opaque. That is, "transparent" means having a visible light transmittance greater than 0% and up to 100%.

[0020] A non-limiting transparency 10 incorporating features of the present invention is shown in FIG. 1A. The transparency 10 can have any desired visible light, infrared, or ultraviolet transmission and / or reflection.

[0021] The exemplary transparent article 10 of FIG. 1A is in the form of a conventional insulating glass unit and includes a first pane 12 having a first major surface 14 (a first surface) and an opposing second major surface 16 (a second surface). In the illustrated non-limiting embodiment, the first major surface 14 faces the exterior of the building, i.e., is an outer major surface, and the second major surface 16 faces the interior of the building. The transparent article 10 also includes a second pane 18 having an inner (first) major surface 20 (a third surface) and an outer (second) major surface 22 (a fourth surface), the second pane 18 being spaced from the first pane 12. This numbering of the pane surfaces is consistent with conventional practice in the fenestration art. The first and second panes 12, 18 can be connected in any suitable manner, such as by adhesively bonding to a conventional spacer frame 24. A gap or chamber 26 is formed between the two panes 12, 18. The chamber 26 can be filled with a selected atmosphere such as air, or a non-reactive gas such as argon or krypton gas. A solar control coating 30 (or any of the other coatings described below) is formed on at least a portion of one of the panes 12, 18, for example, but not limited to, at least a portion of the second surface 16 or at least a portion of the third surface 20. However, if desired, the coating can also be on the first surface or the fourth surface. Examples of insulating glass units can be found, for example, in U.S. Patent Nos. 4,193,236, 4,464,874, 5,088,258, and 5,106,663.

[0022] The exemplary transparent object of FIG. 1B is in the form of a conventional transparent object 110 for a vehicle, such as a window or a sunroof. For clarity, seals, connectors, and opening mechanisms are not shown, nor is a complete vehicle shown. The transparent object includes a first ply 112 having a first major surface 114 (first surface) and an opposing second major surface 116 (second surface) attached to the vehicle body 118 (partially shown) of the vehicle. In the illustrated non-limiting embodiment, the first major surface 114 faces the exterior of the vehicle, i.e., the outer major surface, and the second major surface 116 faces the interior of the vehicle. Non-limiting examples of the vehicle body include the roof of an automobile in the case of a sunroof, the door or frame of an automobile in the case of an automobile window, or the fuselage of an airplane. The transparent object may be attached to a mechanism that can open and close a transparent object such as a vehicle window or a sunroof, as is widely known in the vehicle art. Although either a solar control coating 130 or any of the other coatings described herein is shown as being formed on the first surface 114, it may be formed on at least a portion of the second surface 116.

[0023] In a broad implementation of the present invention, the primings 12, 18, 112 of the transparent objects 10, 110 can be of the same or different materials. The primings 12, 18, 112 can include any desired material having any desired properties. For example, one or more of the primings 12, 18, 112 can be transparent or translucent to visible light. "Transparent" means having a visible light transmittance greater than 0% and up to 100%. Alternatively, one or more of the primings 12, 18, 112 can be translucent. "Translucent" means allowing electromagnetic energy (e.g., visible light) to pass through, but diffusing this energy so that the object on the opposite side from the viewer cannot be clearly seen. Examples of suitable materials include plastic substrates (e.g., acrylic polymers such as polyacrylates; polyalkyl methacrylates such as polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, etc.; polyurethanes; polycarbonates; polyalkyl terephthalates such as polyethylene terephthalate (PET), polypropylene terephthalate, polybutylene terephthalate, etc.; polysiloxane-containing polymers; or copolymers of any monomers for preparing these, or any mixtures thereof); ceramic substrates; glass substrates; or mixtures or combinations of any of the above, but not limited thereto. For example, one or more of the primings 12, 18, 112 can include conventional soda-lime silicate glass, borosilicate glass, or lead glass. The glass can be clear glass. "Clear glass" means non-tinted or non-colored glass. Alternatively, the glass can be tinted or otherwise colored glass. The glass can be annealed glass or heat-treated glass. As used herein, the term "heat treatment" means quenching or at least partial quenching. The glass can be of any type such as conventional float glass and can be of any composition having any desired values of any optical properties, e.g., visible transmittance, ultraviolet transmittance, infrared transmittance, and / or total solar energy transmittance."Float glass" means glass formed by a conventional float process in which molten glass is deposited on a molten metal bath and controllably cooled to form a float glass ribbon. Examples of the float glass process are disclosed in U.S. Patent Nos. 4,466,562 and 4,671,155.

[0024] Plies 12, 18, 112 can each, for example, include clear float glass or can be tinted or colored glass, where one of plies 12, 18 can be clear glass and the other of plies 12, 18 can be colored glass. By way of non-limiting example, examples of glass suitable for the first ply 12 and / or the second ply 18 are described in U.S. Patent Nos. 4,746,347; 4,792,536; 5,030,593; 5,030,594; 5,240,886; 5,385,872; and 5,393,593. Plies 12, 18, 112 can be of any desired dimensions, such as length, width, shape, or thickness. In one exemplary automotive transparency, the first and second plies can each be from 1 mm to 10 mm thick, such as from 1 mm to 8 mm thick, such as from 2 mm to 8 mm, such as from 3 mm to 7 mm, such as from 5 mm to 7 mm, such as 6 mm thick.

[0025] In non-limiting embodiments of the coated articles described herein, the solar control coatings 30, 130 of the present invention are deposited on at least a portion of at least one major surface of the glass plies 12, 18, 112. In the example according to FIG. 1A, the coating 30 is formed on at least a portion of the inner surface 16 of the outer glass plies 12, 112, and further or alternatively, in a non-limiting example consistent with the present disclosure, it should be understood that the coating may be formed on at least a portion of the inner surface 20 of the inner glass ply 18. As used herein, the term "solar control coating" refers to a coating composed of one or more layers or films that affect the solar properties of the coated article, such as, but not limited to, the amount of solar radiation, such as visible, infrared, or ultraviolet, reflected from, absorbed by, or passing through the coated article, the shading coefficient, the emissivity, etc. The solar control coating 30 can block, absorb, or filter selected portions of the solar spectrum, such as, but not limited to, the IR, UV, and / or visible spectra.

[0026] The coatings described herein, such as the solar control coatings 30, 130, can be deposited by any useful method, not limited to these, such as conventional chemical vapor deposition (CVD) and / or physical vapor deposition (PVD) methods. Examples of CVD processes include spray pyrolysis. Examples of PVD processes include electron beam evaporation and vacuum sputtering (such as magnetron sputter deposition (MSVD), etc.). Other coating methods, such as sol-gel deposition, but not limited to this, can also be used. In one non-limiting embodiment, the coatings 30, 130 are deposited by MSVD. Examples of MSVD coating devices and methods are well understood by those skilled in the art and are described, for example, in U.S. Patent No. 4,379,040, U.S. Patent No. 4,861,669, U.S. Patent No. 4,898,789, U.S. Patent No. 4,898,790, U.S. Patent No. 4,900,633, U.S. Patent No. 4,920,006, U.S. Patent No. 4,938,857, U.S. Patent No. 5,328,768, and U.S. Patent No. 5,492,750.

[0027] Figure 2 schematically shows an example of a coated article 200 according to the present disclosure. The coated article includes a substrate 210. The substrate 210 can include any desired properties and can be of any desired thickness. The substrate 210 can include, for example, but not limited to, any suitable transparent material such as the polymers, glasses, and / or ceramic substrates described above in the context of Ply 12, 18, and 112. In a non-limiting example, the substrate 210 can include a glass substrate as described above with reference to Ply 12, 18, 112 as shown in FIG. 1A or FIG. 1B. However, it should be understood that the present invention is equally applicable to other substrates, such as those used in solar cells.

[0028] The functional layer 220 is disposed on at least a part of the base material 210. As used in FIGS. 2 to 6, the functional layers 220, 320, 420, 520 can be any functional coating. For example, it can include one or more dielectric films and / or one or more metal films. Alternatively, the functional layers 220, 320, 420, 520 may include, but are not limited to, a transparent conductive oxide (TCO), as disclosed in, for example, U.S. Patent Application No. 15 / 669,414. The functional layers 220, 320, 420, 520 can include the stacks described in any one of U.S. Patent Application Publication No. 2017 / 0341977, U.S. Patent Application Publication No. 2014 / 0272453, U.S. Patent Application Publication No. 2011 / 0236715, and / or U.S. Patent Application No. 15 / 669,414, or any portion thereof. Except as specifically described below, these exemplary stacks of functional layers are schematically represented by elements 330, 430, 530 in FIGS. 3 to 6, and the details of the embodiments of stacks 330 and 530 are shown in and described with reference to FIGS. 3 to 6 respectively.

[0029] The functional layer may include one or more metal layers. One or more metal films in the functional layers 220, 320, 420, 520 may be composed of silver, gold, palladium, copper, aluminum and / or any mixture and / or alloy of the foregoing. Any metal layer of the functional layers 220, 320, 420, 520 may be continuous or discontinuous.

[0030] One or more metal layers can be continuous layers. The continuous metal layer has a thickness in the range of 50 Å to 200 Å, preferably 55 Å to 150 Å, more preferably 55 Å to 100 Å, and most preferably 60 to 80 Å.

[0031] FIG. 3, FIG. 4A, and FIG. 4B show an example in which the uppermost layer of the functional layer 320 includes a dielectric layer called the uppermost dielectric layer 322 as the uppermost film of the functional layer 320. An example of the uppermost dielectric layer 322 of the functional layer 320 can have a thickness in the range of 50 Å to 750 Å, preferably 250 Å to 600 Å, more preferably, for example, 300 Å to 550 Å, and most preferably 330 Å to 500 Å.

[0032] As shown in FIG. 4B, the uppermost dielectric layer 322 can include a first film 324 shown on any primer layer 328 and a second film 326 that is on the first film and in contact with the protective coating 350. The first film 324 and the second film 326 of the uppermost dielectric layer 322 can be metal oxide, metal nitride, or metal oxynitride films. The metals of the first film 324 and the second film 326 can be titanium, hafnium, zirconium, niobium, zinc, bismuth, lead, indium, tin, aluminum, silicon, and mixtures thereof.

[0033] In a non-limiting embodiment, the first film 324 of the top dielectric layer 322 can be a zinc / tin alloy oxide. The "zinc / tin alloy oxide" means both a true alloy and a mixture of oxides. Zinc oxide can be deposited from a zinc cathode containing other materials to improve the sputtering characteristics of the cathode. Thus, the zinc / tin alloy oxide can be obtained from magnetron sputtering physical vapor deposition from cathodes of zinc and tin. For example, a zinc cathode can contain a small amount (e.g., up to 20 wt%, up to 15 wt%, up to 10 wt%, or up to 5 wt%) of tin, which can improve sputtering. In that case, the resulting zinc oxide film contains a small proportion of tin oxide, e.g., up to 10 wt% of tin oxide, e.g., up to 5 wt% of tin oxide. A coating layer deposited from a zinc cathode having up to 10 wt% tin (added to increase the conductivity of the cathode) is referred to herein as a "zinc oxide film" even if a small amount of tin may be present. One non-limiting cathode can contain zinc and tin in a ratio of 5 wt% to 95 wt% zinc and 95 wt% to 5 wt% tin, e.g., 10 wt% to 90 wt% zinc, and 90 wt% to 10 wt% tin. However, other ratios of zinc and tin can also be used.

[0034] One suitable metal alloy oxide that can be present in the first film 324 or the second film 226 is zinc stannate. "Zinc stannate" means Zn X Sn 1-X O 2-X (the composition of formula 1), where "x" varies in the range greater than 0 and less than 1. For example, "x" can be greater than 0 and can be any fraction or decimal greater than 0 and less than 1. For example, when x = 2 / 3, formula 1 is Zn 2 / 3 Sn 1 / 3 O 4 / 3 and is more generally described as "Zn2SnO4". The zinc stannate-containing film has in the layer a main amount of one or more forms of formula 1.

[0035] Figure 4A discloses an embodiment of a coated article, including a substrate 310, a functional layer 320 according to any aspect or embodiment described herein, and a protective coating 350 including a metal nitride film 356 on the functional layer 320, and a second protective film 360 on the metal nitride film 356. The functional layer includes, for example, a top dielectric layer as shown in FIGS. 3 and 4B. In one non-limiting embodiment, the top dielectric layer 322 may be made of a metal oxide such as zinc stannate. In a further non-limiting embodiment, the top dielectric layer 322 may have a refractive index of 1.5 or more and 2.1 or less. In a further non-limiting embodiment, the top dielectric layer 322 may have a refractive index of 1.7 or more and 1.9 or less, and more preferably 1.8 or more and 1.85 or less.

[0036] As shown in FIG. 4B, in another non-limiting example including a substrate 310, a functional layer 320 including a top dielectric layer 322, an optional primer layer 328, and a stack 330, such as the stack described with reference to FIG. 3, the top dielectric layer 322 of the functional layer 320 may include a first film 324 composed of or consisting of a metal oxide such as zinc oxide deposited on at least a portion of the optional primer layer 328. The second film 326 of the top dielectric layer 322 of the functional layer 320 disposed on at least a portion of the first film 324 may include zinc stannate.

[0037] As shown in FIGS. 3 to 4B, the functional layer 320 may also include an optional primer layer 328 disposed under the dielectric layer 322. The optional primer layer 328 can be a single film or a plurality of film layers. The optional primer layer 328 can include an oxygen scavenging material that can be sacrificed during the deposition process to prevent degradation or oxidation of the metal layer 334 during the sputtering process or subsequent heating process. The optional primer layer 328 can also absorb at least a portion of electromagnetic radiation, such as visible light rays passing through the coating 300. Examples of materials useful for the optional primer layer 328 include titanium, silicon, silicon dioxide, silicon nitride, silicon oxynitride, nickel chromium alloys (such as Inconel), zirconium, aluminum, alloys of silicon and aluminum, alloys containing cobalt and chromium (such as Stellite (registered trademark)), and mixtures of any of the foregoing. In a non-limiting embodiment, the optional primer layer 328 can include titanium deposited as a metal, or titanium and aluminum, and at least a portion of the titanium, or titanium and aluminum, is subsequently oxidized. The optional primer layer 328 can have a thickness in the range of 5 Å to 50 Å, such as 10 Å to 35 Å, such as 15 Å to 35 Å, such as 10 Å to 20 Å, such as 10 Å to 30 Å, such as 20 Å to 30 Å, such as 30 Å to 40 Å. In another example, the optional primer layer 328 can have a thickness in the range of 5 Å to 50 Å, such as 10 Å to 25 Å, such as 15 Å to 25 Å, such as 15 Å to 22 Å, such as 25 Å to 36 Å. As shown, the optional primer layer 328, if present, is disposed in direct contact under the first film 324 of the dielectric layer 322. Although shown in the drawings, it should be understood that the examples according to the present invention do not necessarily include an optional primer layer 328.

[0038] Referring to FIG. 2A, the protective coating 250 is disposed over at least a portion of the functional layer 220 and is the outermost layer of the coated article. The protective coating 250 can help protect the underlying coating layers such as the functional layer 220 and its component films and layers from mechanical and / or chemical attack. FIG. 2B is similar in structure to the coated article shown in FIG. 2A, showing the substrate 210 and the protective coating 250, and including the same first functional layer 220 as the functional layer 220 of FIG. 2A, and a second functional layer 220' disposed under the first functional layer 220 and over the substrate 210. The first functional layer 220 may be the same as or different from the second functional layer 220'. For example, without limitation, the first functional layer 220 includes a dielectric layer, a metal layer over the dielectric layer, and optionally a primer layer over the metal layer, and the uppermost dielectric layer includes a metal oxide film over the metal layer and over the primer layer if the primer layer is present. The second functional layer 220' includes a second dielectric layer over the substrate 210, a second metal layer over the second dielectric layer, and optionally a second primer layer over the second metal layer. In one example, one of the first and / or second metal layers is uncritical. In another example, neither is uncritical. In yet another example, the coated article includes a third functional layer (not shown) that is under the second functional layer 220' and over the substrate 210 and that is the same as or different from either the first or second functional layer 220, 220'. It is noted that multiple small functional layers may be stacked to produce a larger functional layer, which may or may not have properties specific to any particular combination of small functional layers, such as having single silver, double silver, and triple silver coatings, optionally including one or more uncritical silver layers.

[0039] In one embodiment of the present invention, referring to FIG. 4A, the protective layer 350 may include silicon oxide, silicon oxynitride, silicon nitride, a mixture of any two or more of the foregoing, and / or an alloy of any of the foregoing, and may improve the durability of the functional layer 320. The protective layer 350 may include silicon oxide, silicon oxynitride, and / or silicon nitride deposited with another material having excellent conductivity to improve the sputtering of silicon. For example, during deposition, the silicon cathode may include a small amount (e.g., up to 20 wt%, up to 15 wt%, up to 10 wt%, or up to 5 wt%) of aluminum, which can improve sputtering. In that case, the resulting protective layer includes a similar proportion of aluminum, e.g., up to 15 wt% of aluminum, e.g., up to 10 wt% of aluminum, e.g., up to 5 wt% of aluminum. A coating layer deposited from a silicon cathode with up to 10 wt% of aluminum added to increase the conductivity of the cathode is referred to herein as a "silicon oxide", "silicon oxynitride", or "silicon nitride" layer or film even if a small amount of aluminum may be present. A small amount of aluminum (e.g., 15 wt% or less, e.g., 10 wt% or less, e.g., 5 wt% or less) in the cathode is thought to mainly form aluminum nitride in the silicon nitride protective layer 350. In the case of a silicon nitride layer, the protective layer 350 may be formed in a nitrogen atmosphere, but it should be understood that other gases such as oxygen may be present in the atmosphere during deposition of the protective layer 350.

[0040] In another embodiment, referring to FIG. 4B, the protective coating 350 may be composed of a metal oxynitride 354, such as a film of SiON, disposed in contact on top of the uppermost dielectric layer 322 of the functional layer 320, and a metal nitride 356, such as a film of silicon nitride, disposed in contact on top of the metal oxynitride film 354. Examples of the metal oxynitride film 354 may also, or alternatively, include two or more metal nitrides and / or an alloy of one or more metal nitrides. Examples of the metal nitride film 356 may also, or alternatively, include a mixture of two or more metal oxynitrides and / or an alloy of one or more metal oxynitrides. The protective coating 350 may improve the durability of the functional layer 320. The protective coating 350 may be deposited using other materials having excellent conductivity to improve metal sputtering.

[0041] The protective coatings 250, 350 have a total thickness in the range of 320 Å to 800 Å, 420 Å to 800 Å, 400 Å to 700 Å, 500 Å to 800 Å, 600 Å to 700 Å, 580 Å to 630 Å, or 620 Å to 670 Å (i.e., the sum of the thicknesses of all the layers or films within the protective coatings (250, 350)).

[0042] The atomic ratio of oxygen to nitrogen in the metal oxynitride can vary from 0 wt% to 100 wt%, where wt% refers to the ratio of the mass of N or O in the composition excluding the metal of the metal oxynitride to the total mass of N + O. Thus, referring to FIG. 4B, the metal oxynitride film 354 contains 0 wt% nitrogen and up to 100 wt% nitrogen. The metal oxynitride film 354 contains more than 0 wt% oxygen and up to 15 wt% oxygen, up to 10 wt% oxygen, up to 5 wt% oxygen. Non-limiting examples of useful atomic ratios of oxygen to nitrogen in the metal oxynitride layer include, for example, 99.9% to 0.1% N with 0.1% to 99.9% O, 99% to 1% N with 1% to 99% O, or 90% to 10% N with 10% to 90% O, but are not limited thereto.

[0043] In one embodiment, the oxynitride is an oxynitride of the same metal as the metal nitride layer 356 that contacts the metal oxynitride layer 354. In another embodiment, the metal oxynitride layer 354 is a gradient layer, where the portion of the oxynitride layer closest to the top dielectric layer 322 contains a greater amount of oxygen, and the opposite portion of the metal oxynitride layer 354, for example, the portion closest to the metal nitride layer 356, contains a greater amount of nitrogen, for example, in the atomic ratios described above. In one embodiment, the metal oxynitride layer 354 and the metal nitride layer 356 form a continuous single gradient layer. In another embodiment, the metal oxynitride layer 354 is applied over and / or between the metal oxide layer and the metal nitride layer. In another embodiment, the metal nitride layer 356 is absent, the metal oxynitride film 354 is a gradient layer, and the amount of oxygen in the metal oxynitride film decreases as the distance from the top dielectric layer increases. For example, the portion of the oxynitride layer closest to the top dielectric layer 322 contains a greater amount of oxygen, and the opposite portion of the oxynitride layer 354 contains a greater amount of nitrogen, for example, in the atomic ratios described above, for example, but not limited to, 99.9% - 0.1% N with 0.1% - 99.9% O, 99% - 1% N with 1% - 99% O, or 90% - 10% N with 10% - 90% O.

[0044] In the protective coating 350 according to the present disclosure, the metal oxynitride film 354, such as a film composed of silicon oxynitride, may have a refractive index of at least 1.4 and 2.3 or less. In one embodiment, the metal oxynitride film 354 has a refractive index of at least 1.45 and 2.2 or less. In another embodiment, the metal oxynitride film 354 has a refractive index of at least 1.75 and 2.1 or less. In yet another embodiment, the metal oxynitride film 354 has a refractive index of at least 1.8 and 2.1 or less. It should be understood that the refractive index of the metal oxynitride film 354 depends at least in part on the weight percentage of nitrogen present in the metal oxynitride film 354. The protective coating 350 can be the outermost layer of the coated article.

[0045] The metal oxynitride film 354 can have a thickness in the range of >0 Å (greater than 0 Å) to 400 Å, for example, 70 Å to 400 Å, 100 Å to 400 Å, 280 Å to 330 Å, or 110 Å to 130 Å. In embodiments where the metal oxynitride film 354 is the gradient layer, the only film within the protective coating, or there is no metal nitride film within the protective coating, it can have a thickness of 200 Å to 400 Å, preferably 225 Å to 375 Å, more preferably 250 Å to 350 Å, and most preferably 280 Å to 330 Å.

[0046] The metal nitride film 356 can have a thickness in the range of >0 Å (greater than 0 Å) to 400 Å, for example, 70 Å to 400 Å, 100 Å to 400 Å, 250 Å to 400 Å, 280 Å to 330 Å, 200 Å to 250 Å, 200 Å to 400 Å, or 100 Å to 150 Å. In embodiments where there is no metal oxynitride layer and / or no second protective film, the metal nitride film 356 can have a thickness in the range of 100 Å to 400 Å, preferably 250 Å to 400 Å, and most preferably 280 Å to 330 Å. In embodiments where the protective coating has a metal oxynitride film 354 and a second protective layer, the metal nitride film 356 can have a thickness of 100 Å to 400 Å, preferably 150 Å to 330 Å, more preferably 175 Å to 300 Å, and most preferably 200 Å to 250 Å. In embodiments where the protective coating has both a metal nitride 356 film and a second protective film 360, the metal oxynitride film can have a thickness of 50 Å to 200 Å, preferably 75 Å to 175 Å, more preferably 100 Å to 150 Å, and most preferably 110 Å to 130 Å.

[0047] In certain embodiments, the present invention has the combined thickness of the metal oxynitride film 354 (if present) and / or the metal nitride film 356 (if present). The combined thickness can be 200 Å to 800 Å, for example, 320 Å to 800 Å, 320 Å to 370 Å, or 280 Å to 330 Å.

[0048] The combined layer of metal nitride, metal oxynitride, metal nitride, and / or a second protective film, such as TiAlO, can have a thickness in the range of >0 Å (greater than 0 Å) to 1000 Å, for example, 170 Å to 800 Å, 320 Å to 370 Å, 280 Å to 330 Å, 320 Å to 800 Å, 310 Å to 360 Å, 130 Å to 430 Å, 320 Å to 800 Å, or 350 Å to 400 Å.

[0049] Referring to FIGS. 3 and 4B, the metal oxynitride film 354 of the protective coating 350 creates a strong bond between the metal nitride film 356 and the metal oxide of the second film 326 of the uppermost dielectric layer 322 of the functional layer 320. Examples consistent with this disclosure include a silicon nitride film 356 disposed in contact with at least a portion of a silicon oxynitride film 354 disposed in contact with at least a portion of a zinc stannate uppermost dielectric layer 322.

[0050] In examples consistent with this disclosure, it should be understood that silicon in the metal nitride film 356 and / or the metal oxynitride film 354 may be at least partially replaced with oxides, oxynitrides, and nitrides of other metals, respectively. These other metals may be the same or different between the films 354, 356. The metals can be titanium, hafnium, zirconium, niobium, zinc, bismuth, lead, indium, tin, aluminum, silicon, and mixtures thereof.

[0051] Referring to FIGS. 4A and 4B, a coated article according to any aspect or embodiment of the coated articles described herein may include a second protective film 360. The second protective film 360 is shown disposed on the metal nitride film 356 and may include, for example, a metal oxide or metal nitride layer. The second protective film 360 can be titania, alumina, silica, zirconia, tin oxide, mixtures thereof, or alloys thereof. For example, the second protective film 360 may include a mixture of silica and alumina, a mixture of titania and alumina, or zirconia. An example of the second film 360 may include TiAlO. Non-limiting examples of the second protective film 360 may have a thickness in the range of 10 Å to 80 Å, such as 25 to 75 Å, such as 35 Å to 55 Å. It should be understood that the second protective film 360 may be applied, for example as the top layer, to any other configuration of the top dielectric layer, metal nitride, and metal oxynitride film consistent with the present disclosure. Alternatively, an additional functional layer or protective layer may be applied on the second protective film 360. Similarly, it should be understood that the coated article need not include the second protective film 360.

[0052] In a non-limiting example, the coated article may include an additional protective layer (not shown) disposed on the second protective film 360. This additional protective layer can be the protective coating 350, or any material used to form the second protective film 360, or any material that can be used as a top coat.

[0053] Primers such as any of the primers 328 described above may be disposed on and / or in direct contact with any of the metal layers of the functional layer 320 or any metal layer that is a continuous layer. In one non-limiting embodiment, the primer is not in direct contact with a discontinuous (uncritical) metal layer. In this embodiment, the primer is not applied directly on or in direct contact with the discontinuous layer. However, the primer layer may be disposed in direct contact with each of the continuous metal layers. Further, the primer may be titanium or a mixture or alloy of titanium and aluminum such as, but not limited to, titanium aluminide.

[0054] Referring to FIG. 5, the transparent article 400 may include a substrate 410, a functional layer 420, and a protective coating 450. Although not shown, some examples may also include a second protective film 360 (FIG. 4B) according to the present disclosure, but it should be understood that the second protective film 360 may also not be included. In the example shown in FIG. 5, the protective coating 450 may include a second protective film that matches the second protective film 360 disclosed above, or any other configuration or topcoat known in the art that is consistent with this disclosure. The functional layer 420 may include a stack of a metal layer, a dielectric layer, and a primer layer that is consistent with the present disclosure.

[0055] Referring further to FIG. 5, the functional layer 420 includes a top dielectric layer 422. The top dielectric layer 422 may be disposed at least partially on the primer layer 428 in accordance with the present disclosure. In a non-limiting example, the top dielectric layer 422 may consist of a single layer and may have a refractive index of at least 1.5 and 2.1 or less, more preferably at least 1.9 and 1.9 or less, and even more preferably at least 1.8 and 1.85 or less. In an example according to the present disclosure, the top dielectric layer 422 may consist of zinc stannate. The characteristics of the top dielectric layer 422 may be consistent with the characteristics of the top dielectric layer 322. In other examples, the top dielectric layers 322, 422 do not include zinc 90 (including 90% zinc oxide and 10% tin oxide).

[0056] Through careful testing, it has been found that the top dielectric layer 322 containing zinc stannate improves the durability of the stack and reduces corrosion / brightness defects under such conditions. Further, the use of the top dielectric layer 322 made of zinc stannate disposed on the top primer layer 328 of the functional layer 320 does not affect color control. Alternatively, zinc oxide or zinc 90 may be used in the top dielectric layer. Alternatively, the top dielectric layer can have two films, with the lower film being a zinc oxide film and the upper film being a zinc stannate film.

[0057] Referring to FIG. 6, the coated article 500 includes a substrate 510, a functional layer 520 on the substrate 510, and a protective coating 550 on the functional layer 520, according to any embodiment or aspect described herein. The functional layer 520 includes a functional stack 530 including a metal oxide layer 531 according to any embodiment or aspect described herein and a metal layer 534 on the metal oxide layer 531 according to any embodiment or aspect described herein. Any primer layer 528 according to any embodiment or aspect described herein is deposited on the metal layer 534. According to any aspect or embodiment described herein, the functional layer 520 also includes a top dielectric layer 522. The protective coat 550 is a protective coating according to any aspect or embodiment described herein. In one embodiment, the substrate 510 is glass, the metal oxide layer 531 includes a dielectric layer, such as a layer 532 of zinc oxide and a second layer 533 of zinc stannate on the layer of zinc oxide, the metal layer 534 includes or consists of Ag, the primer layer 528 includes or consists of Ti or TiAl, the dielectric layer 522 includes or consists of zinc oxide and / or zinc stannate, and the protective coating 550 includes a metal nitride layer including one or more layers of SiON or Si3N4 on the metal oxide layer 522 and a second protective film 560 on the metal nitride layer 552. In one embodiment, for example, referring to FIG. 6, the metal nitride layer 552 of the protective coating 550 includes a silicon oxynitride layer 554 in contact with the metal oxide layer 522 and a silicon nitride layer 556 in contact with the silicon oxynitride layer 554.

[0058] Tables 1-6 provide examples of useful coated articles according to the present disclosure, including thickness and preferred thicknesses of various layers.

[0059] [Table 1]

[0060] [Table 2]

[0061] [Table 3]

[0062] [Table 4]

[0063] Table 5 - SiON on a dielectric film with a TiAlO protective layer

[0064] [Table 5]

[0065] [Table 6]

[0066] The following provides examples of coated articles according to the present disclosure. However, it should be understood that the present invention is not limited to these specific embodiments.

[0067] Example Examples 1 to 6 are examples of coated articles according to the present invention. This example shows an embodiment in which the functional layer includes two dielectric layers and one metal layer, but according to the present invention, additional dielectric layers and / or metal layers may be present. Further, the example shows an embodiment in which the outermost layer is either a metal oxynitride film, a metal nitride film, or a second protective film, but it is understood that an additional functional coating and / or an additional protective layer can be applied on top of the outermost layer shown in the example. Further, although the example shows a coating on one piece of glass, it is understood that this coating can be applied to laminated glass, automotive glass, insulating glass units, etc.

[0068] Example 1 The substrate is coated with a functional layer. The substrate was glass. The functional layer includes a first dielectric layer, a metal layer, a primer layer, and a second dielectric layer disposed on the substrate. The first dielectric layer includes a zinc stannate film and a zinc oxide film. The metal layer is disposed on the zinc oxide film of the first dielectric layer. The metal layer is a continuous silver layer. The primer layer is disposed on the metal layer, and the second dielectric layer is disposed on the primer layer. The second dielectric layer includes zinc stannate. The protective layer is disposed on the second dielectric layer of the functional layer and includes SiN and a second protective layer disposed on the SiN layer and containing TiAlO. All thicknesses are approximate.

Table 7

[0069] Example 2 The glass substrate is coated with a functional layer. The functional layer includes a first dielectric layer, a metal layer, a primer layer, and a second dielectric layer. The first dielectric layer is disposed on the substrate and includes a zinc stannate film and a zinc oxide film disposed on the zinc stannate film. The metal layer is disposed on the first dielectric layer. The metal layer is a continuous silver layer. The primer layer is disposed on the metal layer. The second dielectric layer is disposed on the primer layer. The second dielectric layer of this exemplary coated article includes a first zinc oxide film and a second zinc stannate film disposed on the first layer. A protective coating is disposed on the functional layer and is in contact with the zinc stannate film of the second dielectric layer. The first protective layer contains SiN. The second protective layer is disposed on the first protective layer and contains TiAlO. All thicknesses are approximate.

Table 8

[0070] Example 3 The substrate is coated with a functional layer. The substrate may be any suitable material such as glass. The functional layer includes a first dielectric layer, a metal layer, a primer layer, and a second dielectric layer disposed on the substrate. The first dielectric layer includes a zinc stannate film and a zinc oxide film. The metal layer is disposed on the zinc oxide film of the first dielectric layer. The metal layer is a continuous silver layer. The primer layer is disposed on the metal layer, and the second dielectric layer is disposed on the primer layer. The second dielectric layer is made of zinc stannate. The protective coating is disposed on the second dielectric layer of the functional layer and includes a SiN layer and a SiON layer disposed between the SiN layer and the dielectric layer. All thicknesses are approximate.

Table 9

[0071] Example 4 The glass substrate is coated with a functional layer. The functional layer includes a first dielectric layer, a metal layer, a primer layer, and a second dielectric layer which is the uppermost layer of the functional layer. The first dielectric layer is disposed on the substrate and includes a zinc stannate film and a zinc oxide film disposed on the zinc stannate film. The metal layer is disposed on the first dielectric layer. The metal layer is a continuous silver layer. The primer layer is disposed on the metal layer. The second dielectric layer is disposed on the primer layer. The second dielectric layer of this exemplary coated article consists of a zinc stannate film. A protective coating is disposed on the functional layer and is in contact with the second dielectric layer of zinc stannate. The protective coating is disposed on the second dielectric layer of the functional layer and includes a SiN layer and a SiON layer disposed between the SiN layer and the dielectric layer. All thicknesses are approximate. The second protective layer is disposed on the SiN layer and includes TiAlO. All thicknesses are approximate.

Table 10

[0072] Example 5 The glass substrate is coated with a functional layer. The functional layer includes a first dielectric layer, a metal layer, a primer layer, and a second dielectric layer. The first dielectric layer is disposed on the substrate and includes a zinc stannate film and a zinc oxide film disposed on the zinc stannate film. The metal layer is disposed on the first dielectric layer. The metal layer is a continuous silver layer. The primer layer is disposed on the metal layer. The second dielectric layer is disposed on the primer layer. The second dielectric layer of this exemplary coated article includes a zinc stannate film. A protective coating is disposed on the functional layer and is in contact with the zinc stannate film of the second dielectric layer. The first protective layer includes SiON. The second protective layer is disposed on the first protective layer and includes TiAlO. All thicknesses are approximate.

Table 11

[0073] Example 6 The glass substrate is coated with a functional layer. The functional layer includes a first dielectric layer, a metal layer, a primer layer, and a second dielectric layer. The first dielectric layer is disposed on the substrate and includes a zinc stannate film and a zinc oxide film disposed on the zinc stannate film. The metal layer is disposed on the first dielectric layer. The metal layer is a continuous silver layer. The primer layer is disposed on the metal layer. The second dielectric layer is disposed on the primer layer. The second dielectric layer of this exemplary coated article includes a zinc stannate film. A protective coating is disposed on the functional layer and is in contact with the zinc stannate film of the second dielectric layer. The first protective layer includes SiON of a gradient film, and in the direction from the zinc stannate film toward the second protective layer including TiAlO disposed on the first protective layer, the N content increases and the O content decreases. All thicknesses are approximate.

Table 12

[0074] The following numbered clauses illustrate various aspects of the present invention.

[0075] Clause 1. A coated article comprising a substrate, a first functional layer on at least a part of the substrate, and a protective coating on at least a part of the functional layer, wherein the topmost layer of the functional layer is a metal oxide film, and the protective coating includes one or more layers of a metal nitride, a metal oxynitride, or a combination thereof.

[0076] Clause 2. The coated article of Clause 1, wherein the metal nitride, the metal oxynitride, or a combination thereof is at least one of silicon nitride, silicon oxynitride, or a combination thereof.

[0077] Clause 3. The coated article of Clause 1, wherein the protective coating includes a metal oxynitride film in contact with at least a part of the metal oxide film of the topmost layer of the first functional layer, and a metal nitride film in contact with at least a part of this metal oxynitride film.

[0078] Item 4. A coated article according to any one of Items 1 to 3, wherein the protective coating comprises a silicon nitride film.

[0079] Item 5. A coated article according to any one of Items 1 to 3, wherein the protective coating comprises a silicon oxynitride film.

[0080] Item 6. A coated article according to Item 3, wherein the metal oxynitride film is a gradient layer, and a part of the metal oxynitride film closest to the top layer of the first functional layer contains more oxygen than a part of the metal oxynitride film closest to the metal nitride film.

[0081] Item 7. A coated article according to Item 1, wherein the protective coating comprises a metal oxynitride film in contact with at least a part of the metal oxide film on the top layer of the first functional layer, and the metal oxynitride film is a gradient layer, where the amount of oxygen in the metal oxynitride film decreases as the distance from the top layer of the first functional layer increases, or where a part of the metal oxynitride film closest to the top layer of the first functional layer contains more oxygen than a part of the metal oxynitride film farthest from the top layer of the first functional layer.

[0082] Item 8. A coated article according to Item 7, wherein the metal oxynitride of the gradient layer is silicon oxynitride.

[0083] Item 9. A coated article according to any one of Items 1 to 8, wherein the metal oxide film of the uppermost dielectric layer of the first functional layer contains zinc stannate or zinc oxide, and the metal oxide film is directly below and in contact with the protective coating.

[0084] Item 10. A coated article according to any one of Items 1 to 9, wherein the first functional layer comprises a dielectric layer on at least a part of a substrate, a metal layer on at least a part of the dielectric layer, and a top layer on at least a part of the metal layer.

[0085] Item 11. A coated article according to Item 10, wherein the first functional layer further comprises a primer layer above the metal layer and below at least a part of the top layer.

[0086] Clause 12. A coated article of Clause 10 or 11, wherein the dielectric layer comprises one or more layers containing zinc oxide and / or zinc stannate, the metal layer comprises Ag, Cu, Au, and / or Pd, and / or the topmost layer contains zinc oxide and / or zinc stannate.

[0087] Clause 13. A coated article of Clause 12, wherein the topmost layer of the functional layer does not contain zinc oxide.

[0088] Clause 14. A coated article of any one of Clauses 1 to 13, further comprising a second functional layer under at least a part of the first functional layer and over at least a part of the substrate.

[0089] Clause 15. A coated article of Clause 14, wherein the second functional layer comprises a second dielectric layer, a second metal layer on the second dielectric layer, and optionally a second primer layer on the metal layer.

[0090] Clause 16. A coated article of any one of Clauses 1 to 15, further comprising a second protective film disposed at least partially over one or more layers of a metal nitride, a metal oxynitride, or a combination thereof, the second protective film comprising at least one of titania, alumina, silica, zirconia, a mixture of any two or more thereof, or an alloy of any one or more thereof.

[0091] Clause 17. A coated article of Clause 16, wherein the second protective film contains TiO2 and / or TiAlO.

[0092] Clause 18. A coated article of any one of Clauses 1 to 17, wherein the functional layer comprises a metal layer and a primer layer over at least a part of the metal layer.

[0093] Clause 19. A coated article of Clause 18, wherein the primer layer contains titanium or titanium and aluminum, and after titanium or titanium and aluminum is deposited on the metal layer, at least a part of the titanium or titanium and aluminum is optionally oxidized.

[0094] Article 20. The coated article of Article 18, wherein the metal layer comprises silver, gold, palladium, copper, or a mixture of any of the foregoing.

[0095] Article 21. The coated article of any one of Articles 18 to 20, wherein the metal layer is a continuous metal film.

[0096] Article 22. The coated article of any one of Articles 18 to 21, wherein the metal layer comprises silver, copper, or a mixture thereof.

[0097] Article 23. A coated article of Article 1, comprising a glass substrate, a first layer of zinc stannate on at least a part of the glass substrate, a layer of zinc oxide on at least a part of the layer of zinc stannate, a layer of silver on at least a part of the layer of zinc oxide, a primer layer containing Ti, TiAl and / or an oxide thereof on at least a part of the layer of silver, a second layer of zinc stannate or zinc oxide on at least a part of the primer layer, a metal oxynitride layer containing silicon nitride directly above at least a part of the second layer of zinc stannate, a metal nitride layer containing silicon directly above at least a part of the metal oxynitride layer, and a second protective layer containing Ti, TiAl, and / or an oxide of any of the foregoing on at least a part of the metal nitride layer.

[0098] Article 24. A coated article of Article 1, comprising a glass substrate, a first layer of zinc stannate directly above at least a part of the glass substrate, a layer of zinc oxide directly above at least a part of the layer of zinc stannate, a layer of silver directly above at least a part of the layer of zinc oxide, a primer layer containing Ti, TiAl and / or an oxide of any of the foregoing on at least a part of the layer of silver, a second layer of zinc stannate on at least a part of the primer layer, a metal oxynitride layer containing silicon directly above at least a part of the second layer of zinc stannate, a metal nitride layer containing silicon directly above at least a part of the metal oxynitride layer, and a second protective layer containing TiAlO on at least a part of the metal nitride layer.

[0099] Clause 25. A coated article of Clause 1, comprising a glass substrate, a first layer of zinc stannate having a thickness in the range of 250 Å to 400 Å on at least a part of the glass substrate, a layer of zinc oxide having a thickness in the range of 70 Å to 90 Å on at least a part of the layer of zinc stannate, a layer of silver having a thickness in the range of 70 Å to 90 Å on at least a part of the layer of zinc oxide, a primer layer containing Ti having a thickness in the range of 10 Å to 30 Å on at least a part of the layer of silver, a second layer of zinc stannate having a thickness in the range of 30 Å to 100 Å on at least a part of the primer layer, a metal oxynitride layer containing SiON and having a thickness in the range of 70 Å to 400 Å immediately above at least a part of the second layer of zinc stannate, a metal nitride layer containing SiN and having a thickness in the range of 100 Å to 400 Å immediately above at least a part of the metal oxynitride layer, and a second protective layer containing TiAlO and having a thickness in the range of 100 Å to 400 Å on the metal nitride layer.

[0100] Clause 26. A coated article of any one of Clauses 1 to 25 attached to a vehicle body.

[0101] Clause 27. A coated article of Clause 26 attached to an automobile as a sunroof.

[0102] Clause 28. A coated article of any one of Clauses 1 to 25 attached to a heat-insulating glass unit.

[0103] Clause 29. A coated article, comprising a substrate, a functional layer having a top layer on at least a part of the substrate, and a protective coating on at least a part of the functional layer, wherein the top layer of the functional layer is a dielectric layer having a refractive index of at least 1.5 and 2.1 or less.

[0104] Clause 30. A coated article of Clause 29, wherein the top layer of the functional layer is made of zinc stannate.

[0105] Clause 31. A coated article of Clause 29, wherein the top layer of the functional layer does not contain zinc oxide.

[0106] Article 32. A coated article comprising a substrate, a functional layer on at least a part of the substrate, and a protective coating on at least a part of the functional layer, wherein the functional layer comprises at least one metal layer and a primer layer disposed at least partially in contact with at least a part of the at least one metal layer, the top layer of the functional layer is disposed in contact with at least a part of the primer layer, and the top layer of the functional layer does not contain zinc oxide.

[0107] Article 33. A heat-insulating glass unit comprising a first ply having a first surface and a second surface, a second ply having a third surface and a fourth surface, and a coating comprising the functional layer and the protective coating according to any one of Articles 1 to 31, wherein the coating is disposed on at least a part of the second surface or the third surface.

[0108] Article 34. The heat-insulating glass unit according to Article 33, wherein the coating is disposed on the second surface.

[0109] Article 35. The heat-insulating glass unit according to Article 33 or 34, further comprising a space between the second surface of the first ply and the third surface of the second ply, the space being filled with a gas.

[0110] Article 36. The heat-insulating glass unit according to Article 35, wherein the gas is argon.

[0111] Article 37. An automotive glass article comprising a first ply having a first surface and a second surface, and a coating comprising the functional layer and the protective coating according to any one of Articles 1 to 31, wherein the coating is disposed on at least a part of the first surface or the second surface.

[0112] Article 38. The automotive glass article according to Article 34, wherein the coating is disposed on the second surface.

[0113] It will be readily understood by those skilled in the art that modifications can be made to the present invention without departing from the concepts disclosed in the foregoing description. Accordingly, the specific embodiments described in detail herein are merely illustrative and not limiting of the scope of the present invention, and the full scope of the appended claims and all equivalents thereof should be given.

Claims

1. A coated article comprising a substrate, a first functional layer on at least a portion of the substrate, and a protective coating on at least a portion of the functional layer, wherein the topmost layer of the functional layer is a metal oxide film, and the protective coating comprises one or more layers of a metal nitride, a metal oxynitride, or a combination thereof.

2. The coated article according to claim 1, wherein the metal nitride, the metal oxynitride, or the combination thereof is at least one of silicon nitride, silicon oxynitride, or a combination thereof.

3. The coated article according to claim 1, wherein the protective coating comprises a metal oxynitride film in contact with at least a portion of the metal oxide film of the topmost layer of the first functional layer, and a metal nitride film in contact with at least a portion of the metal oxynitride film.

4. The coated article according to any one of claims 1 to 3, wherein the protective coating comprises a gradient metal oxynitride film in contact with at least a portion of the metal oxide film of the topmost layer of the first functional layer, and the amount of oxygen in the metal oxynitride film decreases as the distance from the topmost layer of the first functional layer increases, and the metal oxynitride of the gradient layer is optionally silicon oxynitride.

5. The coated article according to any one of claims 1 to 4, wherein the metal oxide film of the topmost dielectric layer of the first functional layer comprises zinc stannate.

6. The coated article according to any one of claims 1 to 5, wherein the first functional layer comprises a dielectric layer on at least a portion of the substrate, a metal layer on at least a portion of the dielectric layer, and a topmost layer on at least a portion of the metal layer.

7. The coated article according to claim 6, wherein the first functional layer further comprises a primer layer above the metal layer and below at least a portion of the topmost layer.

8. The coated article according to claim 7, wherein the primer layer comprises titanium or titanium and aluminum, and after the titanium or titanium and aluminum is deposited on the metal layer, at least a portion of the titanium or titanium and aluminum is optionally oxidized.

9. The coated article according to claim 6, wherein the dielectric layer contains zinc oxide and / or zinc stannate, the metal layer contains Ag, Cu, Au, and / or Pd, and / or the outermost layer contains zinc stannate.

10. The coated article according to any one of claims 1 to 9, wherein the outermost layer does not contain zinc oxide.

11. The coated article according to any one of claims 1 to 9, further comprising a second functional layer under at least a part of the first functional layer and over at least a part of the substrate.

12. Further comprising a second protective film disposed at least partially over one or more layers of metal nitride, metal oxynitride, or a combination thereof, The coated article according to any one of claims 1 to 11, wherein the second protective film contains at least one of titania, alumina, silica, zirconia, an alloy of any one or more of these, or a mixture of any of these.

13. A glass substrate, A first layer of zinc stannate over at least a part of the glass substrate, A layer of zinc oxide over at least a part of the layer of zinc stannate, A layer of silver over at least a part of the layer of zinc oxide, A primer layer containing Ti, TiAl, and / or an oxide thereof over at least a part of the layer of silver, A second layer of zinc stannate or zinc oxide over at least a part of the primer layer, A metal oxynitride layer containing SiON directly over at least a part of the second layer of zinc stannate, A metal nitride layer containing silicon directly over at least a part of the metal oxynitride layer, and A second protective layer containing Ti, TiAl, and / or an oxide of any of these over at least a part of the metal nitride layer, The coated article according to claim 1.

14. A glass substrate, A first layer of zinc stannate directly over at least a part of the glass substrate, A layer of zinc oxide directly over at least a part of the layer of zinc stannate, A layer of silver directly over at least a part of the layer of zinc oxide, A primer layer containing Ti, TiAl, and / or an oxide of any of these directly over at least a part of the layer of silver, A second layer of zinc stannate directly over at least a part of the primer layer, A metal oxynitride layer containing silicon directly over at least a part of the second layer of zinc stannate, A metal nitride layer containing silicon directly over at least a part of the metal oxynitride layer, and A functional layer including a second protective layer containing TiAlO directly above at least a part of the metal nitride layer The coated article according to claim 1

15. A glass substrate A first layer of zinc stannate having a thickness in the range of 250 Å to 400 Å on at least a part of the glass substrate A layer of zinc oxide having a thickness in the range of 70 Å to 90 Å on at least a part of the layer of zinc stannate A layer of silver having a thickness in the range of 70 Å to 90 Å on at least a part of the layer of zinc oxide A primer layer containing Ti having a thickness in the range of 10 Å to 30 Å on at least a part of the layer of silver A second layer of zinc stannate having a thickness in the range of 30 Å to 100 Å on at least a part of the primer layer A metal oxynitride layer containing SiON and having a thickness in the range of 70 Å to 400 Å directly above at least a part of the second layer of zinc stannate A metal nitride layer containing SiN and having a thickness in the range of 100 Å to 400 Å directly above at least a part of the metal oxynitride layer, and A functional layer including a second protective layer containing TiAlO and having a thickness in the range of 100 Å to 400 Å on the metal nitride layer The coated article according to claim 1

Images